Surface active rosin derivatives



Patented Apr. 2, 1946 SURFACE ACTIVE ROS IN DERIVATIVES Donald Price,New York, N. Y., and Everette L. v

May, Chevy Chase, 'Md., assignors to National Oil Products Company,Harrison, N. J., a corporation of New Jersey No Drawing. Originalapplication September 13,

1941, Serial No. 410,778. Divided and this application December 6, 1944,Serial No. 566,958

I 4 Claims. (Cl. 2605-99 This invention relates to derivatives of rosinand allied compounds and more particularly to novel sulfonatedderivatives havingexcellent surface active properties and tocorrelated'improvements in the preparationof such products. The

subject matter of the present invention is closely relate to applicationof Price and May, Serial No.

rosin derivatives and the sulfonation products thereof are disclosed andclaimed and the present application is a division of the Price and Mayapplication Serial No. 410,778, filed September 13, 1941, and entitledSurface active rosin derivatives, now Patent No. 2,376,381, issued May22, 1945. Q

Rosin and allied materials afford a cheap source of uniform and reactiveorganic raw material and numerous products are at the present timemanufactured from these substances. However, there have not heretoforebeen developed any rosin products, other than the rosin soaps,possessing in any substantialdegree the properties of detergency,wetting power and foamingpower.

It is accordingly an object of this invention to provide novelderivatives of rosin and allied substances which will possess theseproperties;

This object and others have been achieved by this invention in productswhich are formed by the sulfonation and alkylation of rosin and likesubstances. Preferably, each molecule of the product will contain onesulfonic group and one alkyl group of substantial length, but each rosinmolecule may contain two or more of either or both of these groups. Theproducts may be made by sulfonating the rosin compound. and thereafteralkylating; or both reactions may be carried out concurrently. Thepresent invention is confined to rosin compounds alkylated in thepresence of a strong sulfonating agent, other analogous compounds beingcovered in the afore-' said patents of Price and May.

Rosin has been cited hereinabove as an example of araw material for themanufacture of products according to this invention. However, instead ofrosin, hydrogenated, dehydrogenated, disproportionated or decarboxylatedrosin, or rosin oils may be employed. Likewise suitable are the rosinacids corresponding to the foregoing compounds, such as, for exampl,iibietic, pimaric, sapinlc and the like acids. Si I arly, the glyceryl,glycol, ethylene glycol, diethylene glycol, methyl, ethyl, propyl,butyl, pentaerythritol and other esters of rosin or rosin acids, or ofhydrogenated,

dehydrogenated or' disproportionated rosin .or rosin acids may beemployed. Examples of these are hydrogenated, dehydrogenated, anddisproportionated ester gum; the glyceryl, glycol, ethylene glycol,diethylene glycol, methyl, ethyl, propyl, butyl, pentaerythritol andlike esters of abietic, dihydroabietic anddehydroabietic acids.Hereinafter all the foregoing and, allied substances will be termedgenerically in this specification and the appended claims as rosincompounds}? v I d Coming now to the alkylation of the rosin compoundswhich may optionally have been sulfohated beforehand, the alkyl group tobe combined with the rosin substance maybe any alkyl or aralkyl groupcontaining upwards of 8 and preferably between 10 and 14 carbon atoms.Such groups may be furnished as alcohols, alkenes or naphthenes and maybe condensed with the rosin material by means of any appropriate strongsulfonating agent, such as sulfuric acid, oleum'o'r chlorsulfonic acid.,The temperature at which the condensation is carried out may vary fromabout 20 C. to 50 C. and the reaction will-be completed in about 2 to 6hours, usually between about 2% and 4 hours.

Suitable alcohols for furnishing the alkyl constituent include alcoholscontaining 8 or more and preferably from 10 to 14 carbon'atoms such asoctyl; nonyl, decyl, undecyl, lauryl, myristyl and the like alcohols; orany mixture of alcohols meeting the above requirements such as the mixedalcohols derived by hydrogenation of the fatty residues of various oilssuch as'co'conut oil,

babassu oil, soybean oil and the like. Suitable alkenes may be derivedby any conventional rocess such as the dehydration of the above alcoholsor may be obtainedfrom petroleum prod reaction, in which case thesulfonation may either precede or follow the alkylat'ion step-asdescribed above" and may be accomplished by means of any usualsulfonating agent, such as sulfuric acid,

oleum sulfur t'rioxide, chlorsulfonic acid and the like. This reactionmay conveniently be carried out by-slowly mixing oleum with thealkylated or unalkylated rosin material, dissolved, if desired, in aninert solvent, and maintaining the mixture at room or only slightlyelevated temperature for from about to about 3 hours, after which themixture is neutralized and the sulfonated product is isolated, ifdesired, by extracting it by means of suitable solvents from theneutralized mass.

Products prepared as above outlined are all readily soluble in water toform solutions which have excellent detergent and-foaming propertiesand. exert powerful wetting and penetrating They are further highlyresistant to and alkalinity in the media in which they are employed.These properties adapt actions. hardness, acidity,

the products tomany industrial and domestic uses, such as scouring,leveling, dye penetrating and introfying,'laundering, cleaning ofvarious solid surfaces, removal of spray residues from fruit andproduce,'formation of emulsions for spraying, waxing, etc.,stabilization of latex and many other uses of a like nature.

With the above general discussion in mind,

there are set forth below specific examples of the manufacture ofproducts according to this invention, as illustrative and notinanylimiting sense. All parts given are by weight.

Example I I 10 parts (1 mol)v of rosin and 6 parts (1 mol) of laurylalcohol were mixed and warmed on a water bath until a homogeneousmixture was obtained. The mixture was cooled to 20 C. and 14 were addedslowly with stire ring at temperatures maintained between 20 C.

parts of 20% oleum and 30 C. The reaction was completed by stirring atroom temperature for 3 hours, after which the mass was poured into 45parts of 30 B. NaOH and the pH was adiusted to 8.5. The neutralized masswas evaporated to dryness. The resulting product, which containedmonolauryl rosin monosulfonate as the active ingredient, was aneiilcient detergent characterized by strong foaming, wetting andpenetrating powers.

Example II 10 parts (1 mol) of rosin and 6 parts (1 mol) of the alcoholsderived by the reduction of coconut oil fatty acids were mixed andwarmed on a water bath until a homogeneous mixture was obtained. Themixture was cooled to 20 C. and 14 parts of 20% oleum were addedgradually with stirring at temperatures maintained between 20 C. and 30C. The reaction was completed by stirring at room temperature for 3hours, after which the mass was poured into 45 parts of 30 B. NaOH andthe pH was adjusted to 8.5. The n :utralized mass was evaporated todryness. The product exhibited excellent wetting and detergentproperties.

7 Example III 10 parts (1 mol) of rosin and parts (1 mol) of decanolwere mixed and warmed on a water bath until a homogeneous mixture wasobtained. The mixture was cooled to 20 C. and 14 parts of 20% oleum wereadded slowly with stirring at temperatures maintained between 20 C. and30 C. The

' reaction was completed by stirring at room temperature for 3 hours,after which the mass was poured into 45 parts of 30 B. NaOH and the pHwas adjusted to 8.5. The neutralized mass was evaporated to'dryness. Theproduct exhibited excellent wetting and detergent properties.

which examples are to be considered merely Example IV 10yparts (1 mol)of rosin, 7 parts (1 mol) of myristyl alcohol and 7 parts of ethylenedichloride were mixed and warmed on a water bath unti1 a homogenousmixture was obtained. The mixture was cooled to 20 C. and 14 parts of20% oleum were added gradually with stirring at temperatures maintainedbetween 20 C. and 30C. The reaction was completed by stirring at roomtemperature for 3 hours, after which the mass was poured into 45 partsof 30 B. NaOH and the pH was adjusted to 8.5. The neutralized mass wasevaporated to dryness. The product exhibited excellent wetting anddetergent properties.

Example V 10 parts (1 mol) of dehydroabietic acid (Galex manufactured bythe National Rosin Oil and Size Co. of Savannah, Georgia) and 12 parts(2 mols) of the alcohols derived by the reduction of coconut oil fattyacids were mixed and warmed on a water bath until a homogeneous mixturewas obtained. The mixture was cooled to 20 C. and

18 parts of 20% oleum were added slowly with stirring at temperaturesmaintained between 20 C. and 25 C. The reaction was completed bystirring at room temperature for 3 hours, after which the mass waspoured into 60 parts of 30 B. NaOH and the pH was adjusted to 8.5. Theneutralized mass was evaporated to dryness. The product, the activeingredients of which were sulfonated dehydroabietic acids largelydialkylated with the coconut oil fatty residues, exhibited excellentdetergent powers.

Example VI Abietic acid was substituted for the Galex" in the procedureof Example V. The product was an excellent detergent and wetting agent.

Example VII 10 parts (1 mol) of ester gum, and 6 parts (1 mol) ofcoconut fatty alcohols were warmed, mixed and cooled to 25 C. 14 partsof 20% oleum were added slowly with stirring. Stirring was continued atroom temperature for.3 hours. Thereafter the mass was poured into 45parts of 30 B. NaOH and the pH adjusted to 7.5. The

- neutralized mass-was extracted with butanol and the butanol distilledoff from the extract solution to leave the sulfonated product insalt-free condition. This productwas an excellent detergent. freelysoluble in water.

, Example VIII The procedure of Example VII was followed,

except that the quantity of coconut fatty alcohols was increased to 12parts (2 mols) and the oleum was increased to 18 parts. An excellentsurfaceactiveagent resulted.

Example IX 10 parts (1 mol) of rosin oil and 6 parts (1 mol) of coconutfatty alcohols were warmed, mixed and cooled to 20 C. 18 parts of 20%oleum were added with stirring, the temperature being maintained between15 C. and 25 C. Stirring was continued at room temperature for 3 hours.

Thereafter the mas was poured into 60 parts of 30 B. NaOH and the pHadjusted to 7.5. The mass was evaporated to dryness, leaving asulfonated product having the same excellent properties characteristicof the other products 5 aforementioned.

aacmoa a 3 Example X 6 parts (1 mol) of the trihydrate of dehydroabieticacid sulfonate (fGalex sulfonic acid) and 5.5 parts (2 mols) of thealcohols derived by the reduction of coconut oil fatty acids were mixedand 11 parts of 20% oleum were added with stir,- ring over a. period of30 minutes while maintaining the temperature between 30 and 35 C. Themass was maintained at 35 C. while stirring for three and one-half hoursand then neutralized bypouring the same into 35 parts of 30 B. soda andadjusting the pH to 7.5 to 8.0. The water was evaporated from-the massunder reduced pressure yielding 25 parts of a light-colored solid -(40%active) having excellent detergent properties.

It will thus be seen that there is provided by this invention a class ofsurface active compounds which may be easil and cheaply prepared fromreadily and cheaply procurable starting materials.

These products are all characterized by outstanding detergent, wettingand foaming powers and by their retention of these powers in spite ofthe acidity, alkalinity and hardness of the media in which they areused.

The expression sulionated is used herein to connote both the sulfonieacid derivatives as well as the corresponding alkali metal, ammonium andlike salts thereof.

Since certain changes in carrying out the above process and certainmodifications in the product which embody the invention may be madewithout departing from its scope, it is intended that all mattercontained in the above description shall be interpreted as illustrativeand not in a limiting sense.

It is also to be understood that the following claims are intended tocover all the generic and specific features of the invention hereindescribed and all statements of the scope of the invention which as amatter of language might be said to fall therebetween.

Having described our invention, what we claim as new and desire tosecureby Letters Patent is:

1. A process of producing novel surface active compounds which comprisesreacting a sulfonated compound selected from the group consisting ofsulfonated rosin; sulfonated hydrogenated, sul fonated dehydrogenated,sulfonated dispropon tionated and sulfonated decarboxylated rosin: thefree acids corresponding to sulfonated rosin and sulfonatedhydrogenated; sulfonated dehydrogenated and sulfonated'disproportionated rosin; and esters of the aforementioned acids; with acompound selected from the class consisting of aliphatic alcohols andalkenes having ten to fourteen carbon atoms in the presence of a strongsulfonating agent.

2 A process of producing novel surface active compounds which comprisesreacting a sulfonated rosin with a compound selected from the classconsisting of aliphatic alcohols and alkenes having ten tofourteencarbon atoms in the presence of a strong sulfonating agent.

3. A process of producing novel surface active compounds which comprisesreacting a sulfonated rosin oil with a compoundselected from the classconsisting of aliphatic alcohols and alkenes having ten to fourteencarbon atoms in the presence of a strong sulfonating agent.

4. A process of producing novel surface active compounds which comprisesreacting a sulfonated dehydroabietic acid with a compound selected fromthe class consisting of aliphatic alcohols and alkenes having ten tofourteen carbon atoms in the presence of a strong sulfonating agent.

DONALD PRICE. EVERE'I'I'E L. MAY.

